Detergent composition



v 2,284,856 DETEGENT GQSETEN Goo Colo,

. u vfllue-t-f i as cotton or Maine.

or to New York,

No wins. amelioration may 9, 193%,

Q s. (W. 25%117) invention relates to wetting, detergent end emsln': compositions containing cationectlve compounds and to surface active agents oontemed therein. The invention also includes. wetting end emulsifying processes employing such compounds, textile oils end lubricants, leather fat honoring compositions, cutting oils, scouring compositions, egents, emulsified fat and oil coro oositions, end other types of emulsions prepared therewith es tvell es deznulsifying processes in which petroleum emulsiom or similar emulsions oi weter-in-oil type ere resolved or broken by contact with the cation-active wetting egents.

Most of the wetting agents now in use are of the eulionic acid or sulfuric ester type; that to soy, theyere sulfuric ecid derivatives of carbon-containing substances. All or" the wet egents of this close ere eiuon-sctive, which means the size of their, cottons is relatively small in comparison with the remaining portion or" molecule which becomes negatively charged in solution. Forjesemple such a, powerful wet ting agent as sodium dioctvl sultcsuccinet is believed to dissociate in aqueous solution in the following manner.

l; o,s- -coocoru i n B l from which it is evident that the surface ectivity is due entirely to the characteristics of the onion.

In contrast to the sleeve, the cation surface active compounds of the present invention have s relatively large cation and e, small onion. This causes them to hove distinctive properties in such processes es, for example, the scouring of wool which is negatively charged.

The svett detergent and emulsifying coinnosltions of my invention may he defined as concatlon-sctive compounds of the formula nx zucoon cuvu RiRsN lnvvhich R is on aliphatic radical containing four or more carbon atoms, R1 and Rs are hydrogen, sryl radicals such as nhenyl, tolyl, xyLvl and the like, or methyl, ethyl, propyl, ollyl, hutyl, smyl or similar elwl radicals or hydroxy elkyl redicels such as ethylol, propylol, hutylol and the iii-re. These compounds may be present es the 'sole surface active agent, or they may he used in admixture with fatty acid soaps, sodium sultete or other soluble selts, other wetting agents,- elihhetic alcohols he more than six carbon atoms, pine oil, alpha, pinene, free fatty eclds or the glycerlde oils thereof, and in senerel wherever e wetting and emulsifying agent is repounds in the ouired that is stable under kellnezcondltions.

In. the eloove type formula the surface active commands of my invention hove been dead as contoig tree cerboxylic acid groups. Tins is probably true in most ceses where the wetting composition is employed in e neutral medium, and l have found that the compounds are Well suited for this purpose, One oi the most importent gestures of the invention, however, reoldies in the characteristic behavior or these com presence of acids end ollrelles in which they are readily soluble and to which they ere completely resistant. It is probable that this unusual resistance of the compounds or my invention to colds, elkolies end heat is due, st least in some cases, to on intremoleculor rearrangement with the formation of e lrvdantoin structure, in the following manner neutral, sold or al- However since this hos not-es yet been definitely proved the compounds will he described and claimed on the assumption that they ore free corhoxylic acids or salts thereof.

The elnho-guenido fatty oclcls ore preferably used in the form of the salts which they form with inorganic or strong orgonlc acids, since the solm are in general more soluble than the substituted letty swirl itself. These colts are some whet unusuol since they contoinonly one mole of s nioncbesic sold for each two moles of the guonldo fatty ride has the following empirical iormulo The cstion-sctlve agents of my invention may be prepared according to known methods by reecting o tutty acid of more than three carbon uterus with bromine whereby an ulp-hrom ietty sold is obtained. Qne mole of this bromine substituted fatty acid is then reacted with two moles of on unsubstituted ldine in alcoholic solution at elevated temperetures to form the olphs-guunido fatty acid by the following reaction ecid. For example, the hydrcchlo-' or substituted guenldine nitrate in the presence of sumcient strong alkali to neutralize the acid radical. When two moles of guanidine are used the resulting composition contains an equimolecular mixture of the alpha-guanido fatty acid and guanidine hydrobromide, and is a good wetting and emulsifying agent when used in this form, In many cases, however, it is preferable to separate the alpha-guanido fatty acid and this may be done by crystallization from solvents such as methyl alcohol or in. some cases by extraction of the guanidine salt with hot water, The guanidine and bromine can then be recovered and re-used by treating the guanidine hydrobromide with sodium hydroxide and introducing chlorine into the resulting sodium bromide solution.

Substituted guanidines may be used instead of guanidine itself, as indicated above, whereby the substituted guanidine derivatives are obtained in the same manner. The surface active properties particularly when employed in conjunction with anion-active agents such as sodium lauryl sulfate, sodium dioctyl sulfosuccinate, isopropyl naphthalene sodium sulfonate, sulfuric esters of secondary aliphatic alcohols and the like. I have found that when the above materials are emulsifled in water with the aid of anion-active emulsiof these substituted guanidine derivatives will vary in accordance with the structure and molecular weight of the substituent or substituents, and in this way a wide variety of wetting, emulsifying and detergent agents can be produced.

The surface active properties of the products of my invention are influenced to a considerable extent by the number of carbon atoms in the fatty acid employed as starting material. I have found that such compounds as alpha-guanido butyric and isobutyric acids possess definite surface activity, but that improved surface active properties are obtained as the length of the carbon chain is increased. Thus, for example, the alpha-guanido derivatives of diethyl acetic acid, methyl-n-propyl acetic acid and ethyl-npropyl acetic acid are better wetting agents than is the corresponding derivative of secondary butyl acetic acid. When alpha-guanido derivatives of such fatty acids as caprylic acid, pelargonic acid,

caproic acid, lauric acid, n-tridecylic acid and nmyristic acid are used the composition has both wetting and emulsifying properties to a high degree. Alpha-guanido derivatives of higher fatty acids such as palmitic acid, stearic acid, pentadecatoic acid, margaric acid, arachidic acid and behenic acid may also be used as both wetting and emulsifying agents, and some of these derivatives are very attractive by reason of the low cost of the acids, which may be obtained by the hydrolysis of fats and oils such as palm oil, olive oil and the like, as well as by hydrogenation of fatty acids from cottonseedoil or from the refining of talloel, a by-product obtained'in the digestion of coniferous wood by the Kraft process.

As is indicated above, the surface active agents of the present invention are well suited for the preparation of textile treating compositions of various types. For example the alpha-guanido stearic and palmitic acids and their acid salts such as the nitrate, hydrochloride or sulfate are well suited for scouring and deliming wool in acid solution, either alone or in admixture with other detergents such as pine oil. They may also be used as emulsifying agents in the preparation of wool creams and similar softening agents and lubricants containing, for example, such glyceride oils asteaseed oil, olive oil and the like, or esters such as diethyl or dibutyl phthalate. They may also be incorporated in emulsions of other materials that may be applied to wool such as rubber latex emulsions and the like.

The cation-active agents are also well suited for use in the preparation of paint, wax, lubricating, cosmetic, medicinal and edible fat emulsions,

' blown with air to expel excess bromine.

fying agents and alpha-guanido fatty acids are then added with stirring until a paste of maximum viscosity is obtained, then an extremely stable emulsion is formed. In similar manner, the above materials may also be emulsified in hot water with ordinary soap, after which the alphaguanido fatty acid is added. Further important applications of this nature will be pointed out in the following examples.

The alpha-guanido fatty acids may also be employed as wetting, dispersing or emulsifying agents in the preparation of printinginks, dye baths, photographic emulsions, bituminous emulsions and the like as well as in the resolution of petroleum emulsions and as frothing agents in the froth flotation of ores.

The invention will be described in further detall by the following specific examples, to which however it is not limited. It is understood that while these examples may illustrate in some detail some of the more specific aspects of the invention, they are given primarily for purposes of illustration and the invention in its broader aspects is not limited thereto.

Example 1 Palm oil was saponifled with potassium hy-.

droxide and the soap was decomposed with hydrochloric acid. The resulting aqueous suspension was washed with benzol and then with water until it was neutral to litmus after which thebenzol was distilled off and the palmitic acid collected separately.

An excess of dry bromine was slowly dropped into 75 parts of the palmitic acid which was intimately mixed with 3.5 parts of red phosphorus, the reaction being carried out in sunlight. After addition of the bromine the mixture was heated until fumes of hydrobromic acid had practically ceased whereupon the mixture was The reaction products were then extracted with pe troleum ether and the alphabrom-palmitic acid was allowed to crystallize by spontaneous evaporation.

Guanidine was prepared by dissolving 90 parts of guanidine carbonate in 300 parts of 10% sulfuric acid, diluting with 300 parts of water, and addition of barium hydroxide to precipitate the sulfuric acid and sulfate radical. sulfate was filtered off and the solution was con-' v centrated by vacuum evaporation.

The concentrated guanidine solution was mixed with 20 parts of brom-palmitic acid and '70 parts of ethyl alcohol were added. The mixture was heated in an autoclave at C. for three hours, after which the crude reaction product was obtained as an alcoholic solution. This product was found to possess good wetting and emulsifying properties.

100 parts of raw wool were scoured in a warm bath consisting of 5000 parts water, 36 partshydrochloric acid and 60 parts of the above de-' scribed mixed reaction product. It was found that a good lather was obtained, and that the wool could becleansed in less than 30 minutes. The dried wool possessed an excellent hand, as some of the detergent remained on the fiber.

The barium was filtered off and washed with alcohol.

- aaeaoec Example 2 One mole of alphabrom-isobutyl acetic acid, prepared by the method outlined in Example 1, was mixed with one mole of a hot aqueous guanidine solution containing one moleof sodium hydroxide. The mixture was heated at 60-70 C. for 2% hours, allowed to cool, and the crystalline alpha-guanido isobutyl acetic acid It was recrystallized from hot water and dissolved in dilute hydrochloric acid from which the hydrochloride could be obtained in the form oi fine, needlelike crystals.

Grey cotton cloth which had been lubricated with sulfonated tallow before weaving was washed in a bath containing 1% caustic soda and 0.5% of the alpha-guanido isobutylacetic acid. The lubricant; was completely emulsified and removed from the cloth in a short period or time.

Example 3 Alphabrom-stearic acid was prepared by the reaction of bromine on stearic acid as described in Example 1. 363 parts of this material were heated in an autoclave with an alcoholic solution containing 210 parts of dimethyl guanidine for 4 hours at 110 C. The resulting alphadimethyl guanido stearic acid was separated from the dimethyl guanidine hydrobromide by recrystallization from hot methyl alcohol.

A iatliquoring composition for chrome tanned leather was prepared by agitating a mixture of 2 parts of sulfonated and 1 part unsulfonated teaseed oil and slowly adding a 1% solution of the above described emulsifying agent. A clear and stable emulsion was obtained which possessed excellent lubricating properties for the leather.

Example 4 Alpha-quanido lauric acid was prepared from coconut oil by the method outlined in Example 1. A mixture of 5' parts of this material, parts of sodium dioctyl sulfosuccinate and 85 parts of sodium sulfate were dissolved in a 50% water-alcohol solution and the solvent evaporated by contact with hot air in a commercial spray-drying machine.

The resulting spray-dried mixture was a light,

' flufiy powder constituting an excellent household detergent. When dissolved in hot water it produces copious suds, and the solution was well suited for dishwashing, domestic laundering and the like.

Example 5 Crude talloel or black liquor soap was extracted with a sodium sulfate solution to remove the lignin and acidified with sulfuric acid to liberate a mixture of free fatty acids and abietic acid. After filtration the fatty acids were sepproduced. This product was brominated and heated with a solution containing an equimolecular quantity of guanidine nitrate and twice as much sodium hydroxide,

The resulting product was separated from inorganic salts, dissolved in toluol and used as a demu'lsifying agent for the resolution oi petroleum emulsions of the water-in-oil type. It was found to be particularly eflective in treating emulsions of this type in which the disperse phase was negatively charged, as when the water contained substantial quantities of dissolved salts. Good results were also obtained when the material was used in admixture with phenols.

cresols, hydrochloric acid, and other known de-- RiRaN in which R is an aliphatic radical containing more than three carbon atoms and R1 and R2 are prises washing said textiles in a composition comwater-soluble soali.

prising an aqueous dispersion of .a compound of the formula a-oncoon C:NH mmN in which R is an aliphatic radical containing more than three carbon atoms and Ba and R2 are members of the group consisting of hydrogen andaryl, alkyl and-hydroxyalkyl radicals. and a water-soluble soap.

3. A method of securing wool which comprises washing the wool in an acidic aqueous dispersion of a compound of the formula a-on.coon

H omm RgRgN in which R is an aliphatic radical containing more than three carbon atoms and R1 andRa are members of the group consisting of hydrogen and aryl, alkyl and hydroxyalkyl radicals.

4,. A detergent composition comprising a compound of the formula in which R is an aliphatic radical containing more than three carbon atoms and R1 and R: are members of the group consisting of hydrogen and aryl,, alkyl and hydroxyalkyl radicals, and a WALTER P. ERICKS. 

